WO2021049589A1 - Composition durcissable, ensemble de compositions durcissables à deux liquides et procédé de production d'article lié - Google Patents

Composition durcissable, ensemble de compositions durcissables à deux liquides et procédé de production d'article lié Download PDF

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WO2021049589A1
WO2021049589A1 PCT/JP2020/034364 JP2020034364W WO2021049589A1 WO 2021049589 A1 WO2021049589 A1 WO 2021049589A1 JP 2020034364 W JP2020034364 W JP 2020034364W WO 2021049589 A1 WO2021049589 A1 WO 2021049589A1
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composition
group
compound
curable composition
mass
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Japanese (ja)
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河合　道弘
健人 大村
玄 岡部
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東亞合成株式会社
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Priority to US17/642,078 priority patent/US20220380615A1/en
Publication of WO2021049589A1 publication Critical patent/WO2021049589A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/12—Esters of phenols or saturated alcohols
    • C08F222/14—Esters having no free carboxylic acid groups, e.g. dialkyl maleates or fumarates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/30—Nitriles
    • C08F222/32—Alpha-cyano-acrylic acid; Esters thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/40—Ink-sets specially adapted for multi-colour inkjet printing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/54—Inks based on two liquids, one liquid being the ink, the other liquid being a reaction solution, a fixer or a treatment solution for the ink
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/04—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving separate application of adhesive ingredients to the different surfaces to be joined

Definitions

  • the present invention relates to a curable composition, a two-component curable composition set, and a method for producing an adhesive.
  • the curable composition is widely used in applications such as adhesives, coating agents, encapsulants, and excipients.
  • Polymerization reactions using a curable composition are classified into three types, radical polymerization, cationic polymerization, and anionic polymerization, depending on the active species generated during polymerization.
  • Non-Patent Document 1 shows the results of thermogravimetric analysis of 2-ethyl cyanoacrylate homopolymer and diethyl methylene malonate homopolymer. It has been reported that the 2-ethyl cyanoacrylate homopolymer shows weight loss due to decomposition at a temperature of less than 200 ° C., but the diethylmethylene malonate homopolymer shows almost no weight loss even at 250 ° C. and has excellent heat resistance. ing. Patent Documents 1 and 2 show a method for curing 1,1-dialkoxycarbonylethylene (methylenemalonate). Patent Document 3 discloses a method of adding a Lewis acidic metal salt in order to improve the surface curability and clearance curability of 2-cyanoacrylates.
  • An object to be solved by the present invention is to provide a cured composition having excellent heat resistance of the obtained cured product, or a method for producing an adhesive using the cured composition.
  • Another problem to be solved by the present invention is to provide a two-component curable composition set having excellent heat resistance of the obtained cured product, or a method for producing an adhesive using the two-component curable composition set. That is.
  • Means for solving the above problems include the following aspects. ⁇ 1> A curable composition containing a methylene malonate compound, a 2-cyanoacrylate compound, and a Lewis acidic compound. ⁇ 2> The curable composition according to ⁇ 1>, wherein the methylene malonate compound is a methylene malonate compound represented by the following formula (1) or formula (2).
  • X 1 to X 4 independently represent O, NR, or C (R) 2 , and R independently represents a hydrogen atom, an alkyl group, or an aryl.
  • R 1 and R 2 independently represent an alkyl group or an aryl group
  • R 3 represents an alkylene group, an arylene group, or a group in which two or more of these are combined.
  • the Lewis acidic compound contains a Lewis acidic compound having at least one metal cation selected from the group consisting of Fe 2+ , Cu 2+ , Zn 2+ , Ag + , Yb 3+ , and Ti 4+.
  • the Lewis acidic compound has at least one counter anion selected from the group consisting of trifluoromethanesulfonic acid anion, tert-butoxide anion, acetylacetonate anion, chloride ion, and bromide ion.
  • the content of the Lewis acidic compound is 0.001 part by mass to 1.0 part by mass with respect to 100 parts by mass of the content of the methylene malonate compound represented by the formula (1) or (2).
  • ⁇ 12> A step of applying the curable composition according to any one of ⁇ 1> to ⁇ 11> to the surface of the first adherend, the first subject to which the curable composition is applied.
  • a method for producing an adhesive which comprises a step of adhering a surface of an adhesive and a surface of a second object to be adhered to obtain an adhesive.
  • a composition A containing a 2-cyanoacrylate compound and a composition B containing a Lewis acidic compound are contained, and at least one of the composition A and the composition B further contains a methylene malonate compound 2 Liquid curable composition set.
  • ⁇ 14> The two-component curable composition set according to ⁇ 13>, wherein the methylene malonate compound is a compound represented by the following formula (1) or formula (2).
  • X 1 to X 4 independently represent O, NR, or C (R) 2 , and R independently represents a hydrogen atom, an alkyl group, or an aryl.
  • R 1 and R 2 independently represent an alkyl group or an aryl group
  • R 3 represents an alkylene group, an arylene group, or a group in which two or more of these are combined.
  • the composition A and the composition include the step of adhering the surface of the first adherend to which the composition A and the composition B are applied and the surface of the second adherend to obtain an adhesive.
  • a method for producing an adhesive in which at least one of the substance B further contains a methylene malonate compound.
  • X 1 to X 4 independently represent O, NR, or C (R) 2 , and R independently represents a hydrogen atom, an alkyl group, or an aryl.
  • R 1 and R 2 independently represent an alkyl group or an aryl group
  • R 3 represents an alkylene group, an arylene group, or a group in which two or more of these are combined.
  • the present invention it is possible to provide a cured composition having excellent heat resistance of the obtained cured product, or a method for producing an adhesive using the cured composition. Further, according to the present invention, it is possible to provide a two-component curable composition set having excellent heat resistance of the obtained cured product, and a method for producing an adhesive using the two-component curable composition set.
  • the amount of each component in the composition means the total amount of the plurality of substances present in the composition when a plurality of substances corresponding to each component are present in the composition, unless otherwise specified.
  • the term "process” is included in the present term as long as the intended purpose of the process is achieved, not only in an independent process but also in the case where it cannot be clearly distinguished from other processes.
  • “% by mass” and “% by weight” are synonymous, and “parts by mass” and “parts by weight” are synonymous.
  • a combination of two or more preferred embodiments is a more preferred embodiment.
  • (meth) acryloyl represents both acryloyl and methacryloyl, or either, and “(meth) acryloyl” represents both acryloyl and methacryloyl, or either of them.
  • the hydrocarbon chain may be described by a simplified structural formula in which the symbols of carbon (C) and hydrogen (H) are omitted.
  • imparting means operating so that at least a part of the curable composition comes into contact with the surface of the adherend, or at least a part of the composition A and / and the composition B comes into contact with each other. It means to operate as if to do.
  • a portion or all of the surface of the adherend is covered with a curable composition, or with composition A and / and composition B, using coating, fill-in-the-blanks, and other means. Covering can be exemplified.
  • the contents of the present invention will be described in detail.
  • the curable composition of the present invention contains a methylene malonate compound, a 2-cyanoacrylate compound, and a Lewis acidic compound.
  • the conventional curable composition using a 2-cyanoacrylate compound has an excellent curing rate, but the heat resistance of the cured product is not sufficient.
  • a conventional curable composition containing a methylene malonate compound is cured by a polymerization initiator, or is a basic compound immediately before curing as in the invention described in Patent Document 1 or Patent Document 2. Only the method of mixing was known. As a result of diligent studies, the present inventors have found that a curable composition containing a methylene malonate compound, a 2-cyanoacrylate compound, and a Lewis acidic compound is excellent in heat resistance of the obtained cured product. The present inventors have found.
  • the Lewis acidic compound improves the anionic polymerization activity of the methylenemalonate compound by coordinating with the oxygen atom of one or two carbonyl groups in the methylenemalonate compound, and air. It is presumed that anionic polymerization is possible even with the water content in the compound, and the reaction rate is close to that of the 2-cyanoacrylate compound, so that copolymerization occurs and the heat resistance of the obtained cured product is improved.
  • anionic polymerization of methylene malonate compounds by moisture in the air has not been known at all, and this time, it was discovered for the first time.
  • the curable composition of the present invention contains a methylene malonate compound.
  • the methylene malonate compound is preferably a methylene malonate compound represented by the following formula (1) or (2) from the viewpoint of reaction rate and storage stability, and the following formula (1). It is more preferable that it is a methylene malonate compound represented by.
  • X 1 to X 4 independently represent O, NR, or C (R) 2 , and R independently represents a hydrogen atom, an alkyl group, or an aryl.
  • R 1 and R 2 independently represent an alkyl group or an aryl group
  • R 3 represents an alkylene group, an arylene group, or a group in which two or more of these are combined.
  • X 1 to X 4 in the formulas (1) and (2) are preferably O or NR, respectively, and are O or NR. NH is more preferable, and O is particularly preferable.
  • X 1 and X 2 in the formula (1) are preferably the same group from the viewpoint of heat resistance, reaction rate, and storage stability.
  • X 3 and X 4 in the formula (2) are preferably the same group from the viewpoint of heat resistance, reaction rate, and storage stability.
  • R in the formulas (1) and (2) is independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms (also referred to as "carbon atom number”), or an aryl group having 6 to 20 carbon atoms.
  • NR is particularly preferably NH
  • C (R) 2 is particularly preferably CH 2.
  • R 1 and R 2 in the formula (1) are independently an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms from the viewpoint of heat resistance, reaction rate, and storage stability.
  • R 1 and R 2 in the formula (1) are preferably alkyl groups independently from the viewpoint of heat resistance, reaction rate, and storage stability. Further, R 1 and R 2 in the formula (1) are preferably alkyl groups independently from the viewpoint of heat resistance, reaction rate, and storage stability. Further, R 1 and R 2 in the formula (1) are preferably the same group from the viewpoint of heat resistance, reaction rate, and storage stability.
  • R 3 in the formula (2) contains an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, or an alkylene group having 1 or more and an arylene group having 1 or more carbon atoms. It is preferably a combined group having 7 to 20 carbon atoms, more preferably an alkylene group having 1 to 20 carbon atoms, further preferably an alkylene group having 1 to 10 carbon atoms, and a methylene group and an ethylene group. , Or a dimethylmethylene group is particularly preferable. Further, R 3 in the formula (2) is preferably an alkylene group from the viewpoint of reaction rate.
  • the alkyl group or alkylene group of each group in the formulas (1) and (2) may be linear, has a branch, may have a ring structure, and may have a substituent. You may have.
  • Examples of the substituent that the alkyl group or alkylene group may have include an aryl group, an alkoxy group, an alkoxycarbonyl group, an acyl group and the like.
  • the aryl group or arylene group of each group in the formulas (1) and (2) may have a substituent.
  • Examples of the substituent that the aryl group or arylene group may have include an alkyl group, an aryl group, an alkoxy group, an alkoxycarbonyl group, an acyl group and the like.
  • Preferred specific examples of the methylene malonate compound represented by the formula (1) include, for example, dimethyl 2-methylene malonate, diethyl 2-methylene malonate, dibutyl 2-methylene malonic acid, and 1-methylene malonic acid.
  • Dialkyl 2-methylenemalonate such as methyl-3-hexyl and dicyclohexyl 2-methylenemalonate is preferable.
  • diethyl 2-methylenemalonate is particularly preferable.
  • Preferred specific examples of the methylene malonate compound represented by the formula (2) include, for example, 5-methylene-1,3-dioxane-4,6-dione, 2,2-dimethyl-5-methylene-1, 5-Methylene-1,3-dioxane-4,6-dione compounds such as 3-dioxane-4,6-dione are preferable.
  • the curable composition of the present invention may contain one type of methylene malonate compound alone, or may contain two or more types.
  • the content of the methylene malonate compound in the curable composition of the present invention is 1% by mass to 99% by mass with respect to the total solid content of the curable composition from the viewpoint of heat resistance of the obtained cured product and curing uniformity. It is preferably by mass%, more preferably 5% by mass to 95% by mass, further preferably 10% by mass to 90% by mass, and particularly preferably 20% by mass to 80% by mass. Most preferably, it is 30% by mass to 70% by mass.
  • total solid content means the total mass of a component excluding a solvent from the total composition of a composition.
  • the "solid content” is a component excluding the solvent as described above, and may be, for example, a solid or a liquid at 25 ° C.
  • the curable composition of the present invention contains a 2-cyanoacrylate compound.
  • the 2-cyanoacrylate compound is not particularly limited as long as it is a monomer, but is preferably a compound represented by the following formula (C).
  • R is a saturated or unsaturated linear hydrocarbon group, a branched chain hydrocarbon group or a cyclic hydrocarbon group having 1 to 20 carbon atoms which may have a halogen atom, or , Represents an aromatic hydrocarbon group having 1 to 20 carbon atoms which may have a halogen atom.
  • R contains an ether bond
  • either or both of the ether-bonded hydrocarbon residual chains may have a halogen atom and are saturated or unsaturated with 5 to 20 carbon atoms.
  • It is a chain hydrocarbon group, a branched chain hydrocarbon group, a cyclic hydrocarbon group, or an aromatic group having 5 to 20 carbon atoms which may have a halogen atom.
  • 2-cyanoacrylate compound examples include methyl, ethyl, chloroethyl, n-propyl, i-propyl, allyl, propargyl, n-butyl, i-butyl, n-pentyl, and n-hexyl of 2-cyanoacrylate.
  • 2-cyanoacrylate compounds include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, cyclohexyl, phenyl, tetrahydrofurfuryl, 2-ethylhexyl, and 2-cyanoacrylate compounds.
  • Preferred are n-octyl, 2-octyl, 2-methoxyethyl, 2-ethoxyethyl ester, or 1- (2-methoxy-1-methylethoxy) propyl.
  • the curable composition of the present invention may contain one type of 2-cyanoacrylate compound alone, or may contain two or more types.
  • the content of the 2-cyanoacrylate compound in the curable composition of the present invention is from 1% by mass to the total solid content of the curable composition from the viewpoint of heat resistance of the obtained cured product and curing uniformity. It is preferably 99% by mass, more preferably 5% by mass to 95% by mass, further preferably 10% by mass to 90% by mass, and particularly preferably 20% by mass to 80% by mass. , 30% by mass to 70% by mass, most preferably.
  • the value of the mass ratio (Mc / Mm) of the content Mc of the 2-cyanoacrylate compound and the content Mm of the methylene malonate compound in the curable composition of the present invention is the heat resistance of the obtained cured product. From the viewpoint of curing uniformity, it is preferably 0.05 to 20, more preferably 0.1 to 10, further preferably 0.2 to 5, and 0.5 to 2. It is particularly preferable to have.
  • the curable composition of the present invention contains a Lewis acidic compound.
  • the Lewis acidic compound used in the present invention is preferably a Lewis acidic compound capable of coordinating or acting on the methylene malonate compound.
  • the Lewis acidic compound preferably contains a Lewis acidic compound having a metal cation, and more preferably contains a Lewis acidic compound having a monovalent to tetravalent metal cation. It is preferable to include a Lewis acidic compound having a monovalent to trivalent metal cation, and it is particularly preferable to contain the Lewis acidic compound.
  • group 3 to 12 metal cations are preferable from the viewpoint of curing speed and storage stability, and Fe 2+ , Cu 2+ , Zn 2+ , Ag + , Yb 3+ , Ti 4+ , Zr 4+ , and so on. More preferably, it is at least one metal cation selected from the group consisting of Hf 4+ , In 3+ , Au + , Sn 4+ , Cd 2+ , Ni 2+ , Mn 2+ , Co 2+ , Cr 2+ , Ga 2+, and Fe.
  • it is at least one metal cation selected from the group consisting of 2+ , Cu 2+ , Zn 2+ , Ag + , Yb 3+ , and Ti 4+ , and is composed of Cu 2+ , Zn 2+ , and Ag +. Most preferably, it is at least one metal cation selected from the group.
  • the Lewis acidic compound is preferably a salt of a metal cation and a counter anion from the viewpoint of curing rate and storage stability. Further, the Lewis acidic compound is a group consisting of a sulfonic acid ion, a hypochlorite ion, an alkoxide anion, a 1,3-diketonate anion, and a halide ion from the viewpoint of curing rate and storage stability.
  • a Lewis acidic compound having at least one pair anion selected from, and trifluoromethanesulfonic acid anion, methanesulfonic acid anion, tosylate anion, benzenesulfonic acid anion, hypochlorite anion, tert-butoxide More preferably, it contains a Lewis acidic compound having at least one counter anion selected from the group consisting of anions, acetylacetonate anions, chloride ions, and bromide ions, trifluoromethanesulfonic acid anions, methanesulfonic acid anions.
  • Lewis acid compound having at least one counter anion selected from the group consisting of bromide ion, more preferably trifluoromethanesulfonic acid anion. It is particularly preferable to include a Lewis acidic compound having.
  • the Lewis acidic compound for example, copper (II) trifluoromethanesulfonate, zinc (II) trifluoromethanesulfonate, silver (I) trifluoromethanesulfonate, itterbium (III) trifluoromethanesulfonate, titanium ( IV) Butoxide, titanium (IV) tert-butoxide, copper (II) chloride, copper (II) bromide, zinc (II) chloride, zinc (II) bromide and the like are preferably mentioned.
  • the curable composition of the present invention may contain one type of Lewis acidic compound alone, or may contain two or more types.
  • the content of the Lewis acidic compound in the curable composition of the present invention is 0 with respect to 100 parts by mass of the content of the methylene malonate compound from the viewpoint of heat resistance, curing uniformity, and curing rate of the obtained cured product. It is preferably 0.001 part to 1.0 part by mass, more preferably 0.001 part to 0.5 part by mass, and particularly preferably 0.001 part to 0.1 part by mass. preferable.
  • the curable composition of the present invention preferably contains a polymerization inhibitor, and more preferably contains a radical polymerization inhibitor.
  • the polymerization inhibitor preferably contains a phenolic radical polymerization inhibitor.
  • the phenolic radical polymerization inhibitor include hydroquinone, mequinol, butylhydroxyanisole, di-tert-butylhydroxytoluene, methylhydroquinone, methoxyhydroquinone, 2,6-dimethylhydroquinone, and 2,6-di-tert-butylhydroquinone.
  • examples of the polymerization inhibitor phosphorus pentoxide, SO 2, p-toluenesulfonic acid, methanesulfonic acid, propane sultone, anionic polymerization inhibitors such as BF 3 complex is preferably mentioned.
  • the polymerization inhibitor it is also preferable to use a radical polymerization inhibitor having a hydroquinone structure and an anionic polymerization inhibitor in combination from the viewpoint of storage stability.
  • the polymerization inhibitor preferably contains a polymerization inhibitor having a phenolic hydroxy group, more preferably a compound represented by the following formula (In1), and more preferably a compound represented by the following formula (In2). It is particularly preferable that the compound is represented by. Further, as the polymerization inhibitor, it is particularly preferable to use a radical polymerization inhibitor having a hydroquinone structure, an anionic polymerization inhibitor and a polymerization inhibitor having a phenolic hydroxy group in combination from the viewpoint of storage stability.
  • (In1) and formula (In2) are each R 1 ⁇ R 5 independently represent a hydrogen atom, or a hydroxy group (excluding a phenolic hydroxy group) other than, and bonded to each other to form a ring
  • R 6 represents a hydrogen atom or an alkyl group
  • R 7 to R 10 independently represent an alkyl group, a cycloalkyl group, and an alkenyl group
  • R 11 represents a hydrogen atom or an alkenyl group.
  • R 1 to R 5 is preferably the above-mentioned substituent, and R 1 and R 5 are more preferably at least the above-mentioned substituent. It is particularly preferable that 1 , R 3 and R 5 are at least the above-mentioned substituents.
  • R 1 and R 5 in the formula (In 1) are independently, from the viewpoint of storage stability, an alkyl group having a structure having a linear or branched alkyl group, a cycloalkyl group, a phenolic hydroxy group, or (meth).
  • R 1 is a linear or branched alkyl group
  • R 5 is an alkyl group having a structure having a phenolic hydroxy group, or (meth) acryloxyphenyl. It is more preferable that the alkyl group has a structure, R 1 is a linear or branched alkyl group, and R 5 is an alkyl group having a (meth) acryloxiphenyl structure.
  • R 3 in the formula (In 1) is preferably a hydrogen atom, an alkyl group, or an alkoxy group, and is a linear or branched alkyl group, a cycloalkyl group, or an alkoxy group.
  • the alkyl group in R 1 , R 3 and R 5 is preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and having 1 to 6 carbon atoms.
  • a linear or branched alkyl group, a cycloalkyl group having 1 to 6 carbon atoms, a t-butyl group, or a 2-methyl-2-butyl group is more preferable, and a methyl group, a t-butyl group, or 2 It is particularly preferably a -methyl-2-butyl group.
  • the alkyl group may be linear, has a branch, may have a ring structure, or may have a substituent.
  • the substituent may be a group that does not lose the polymerization inhibitory ability, and examples thereof include a halogen atom, an alkoxy group, and an aryl group. Further, the substituent may be further substituted with at least one group selected from the group consisting of the substituent and the alkyl group.
  • R 2 and R 4 are each independently preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom.
  • R 6 in the formula (In2) is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and more preferably a hydrogen atom or a methyl group.
  • R 7 and R 10 in the formula (In2) are preferably a tertiary alkyl group, more preferably a tertiary alkyl group having 4 to 8 carbon atoms, and t-. It is particularly preferably a butyl group or a 2-methyl-2-butyl group.
  • R 8 and R 9 in the formula (In2) are preferably alkyl groups having 1 to 8 carbon atoms, and are preferably a methyl group, a t-butyl group, a 2-methyl-2-butyl group, and the like. More preferably, it is a methoxy group, an ethoxy group, a propoxy group, or a butoxy group.
  • R 11 in the formula (In2) is preferably a hydrogen atom or a (meth) acryloyl group.
  • the polymerization inhibitor having a phenolic hydroxy group is 2,2'-methylenebis (6-tert-butyl-p-cresol) and 2,2'-methylenebis (4-ethyl-). 6-tert-butyl-phenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol) monoacrylate, 2,2'-ethylenebis (4,6-di-tert-amylphenol) monoacrylate And at least one compound selected from the group consisting of 2,2'-methylenebis (6- (1-methylcyclohexyl) -p-cresol) is preferred.
  • the curable composition of the present invention may contain the polymerization inhibitor alone or in combination of two or more.
  • the content of the polymerization inhibitor in the curable composition of the present invention is 0.01 part by mass with respect to 100 parts by mass in total of the contents of the methylene malonate compound and the 2-cyanoacrylate compound from the viewpoint of storage stability. It is preferably about 20 parts by mass, more preferably 0.05 part by mass to 10 parts by mass, and particularly preferably 0.1 part by mass to 5 parts by mass.
  • the curable composition of the present invention may further contain other components depending on its use.
  • other additives include, for example, fillers, pigments, dyes, leveling agents, defoamers, antistatic agents, ultraviolet absorbers, pH adjusters, dispersants, dispersion aids, surface modifiers, plastics. Examples thereof include accelerators, sagging inhibitors, hardening accelerators, viscosity regulators, antibacterial agents, fluorescent whitening agents, antioxidants and the like. Of these, one type or a combination of two or more types can be used.
  • the other anionic polymerizable compound is not particularly limited as long as the effects of the present invention can be exhibited.
  • a polymerizable epoxy compound for example, a compound having two or more glycidyl groups such as bisphenol A diglycidyl ether
  • the radically polymerizable compound is not particularly limited as long as the effects of the present invention can be exhibited.
  • (meth) acrylate compound, (meth) acrylamide compound and the like can be mentioned.
  • the curable composition of the present invention may contain a polymerization initiator in order to assist or promote curing, and when it contains a radically polymerizable compound, it preferably further contains a radical polymerization initiator, and is a photoradical generator. It is more preferable to further contain.
  • a photoradical generator a known photoradical generator used when photopolymerizing a radically polymerizable compound can be used. Examples of the photoradical generator include an acylgerman compound, an acylphosphine oxide compound, an acetophenone compound having no hydroxy group, nitrogen atom and thioether bond, and a benzoin compound having no hydroxy group, nitrogen atom and thioether bond. Be done.
  • an acyl-Germanic compound is preferable from the viewpoint of photocurability, adhesion speed, and storage stability.
  • acyl Germanic compound a monoacyl Germanic compound and a bisacyl Germanic compound are preferably mentioned, and a bisacyl Germanic compound is more preferably mentioned.
  • acyl-Germanic compound for example, Ivocarin (manufactured by Ivocalar Vivadent) is preferably mentioned.
  • acylphosphine oxide-based compound a monoacylphosphine oxide-based compound and a bisacylphosphine oxide-based compound are preferably mentioned, and a bisacylphosphine oxide-based compound is more preferably mentioned.
  • the curable composition of the present invention may contain one kind of photoradical generator alone or two or more kinds.
  • the content of the polymerization initiator in the curable composition of the present invention is 0.01% by mass to 5% by mass with respect to the total solid content of the curable composition from the viewpoint of photocurability and storage stability. It is preferably 0.05% by mass to 2% by mass, and particularly preferably 0.05% by mass to 1% by mass.
  • the solvent is not particularly limited as long as the effect of the present invention can be exhibited.
  • aromatic hydrocarbon solvents such as benzene, toluene and xylene
  • saturated hydrocarbon solvents such as hexane, cyclohexane and heptane
  • ethers of diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, ethylene glycol monomethyl ether and propylene glycol monomethyl ether are examples of aromatic hydrocarbon solvents such as benzene, toluene and xylene
  • saturated hydrocarbon solvents such as hexane, cyclohexane and heptane
  • ethers of diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, ethylene glycol monomethyl ether and propylene glycol monomethyl ether such as benzene, toluene and xylene
  • Ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate, butyl acetate and propylene glycol monomethyl ether acetate; halogenated hydrocarbon solvents such as chloroform and the like.
  • the content of the solvent shall be 1 part by mass to 1,000 parts by mass with respect to 100 parts by mass in total of the contents of the methylene malonate compound and the 2-cyanoacrylate compound. Is preferable, and it is more preferably 1 part by mass to 500 parts by mass, and particularly preferably 1 part by mass to 300 parts by mass.
  • anionic polymerization accelerator examples include polyalkylene oxides, crown ethers, sila crown ethers, calixarenes, cyclodextrins, pyrogallol-based cyclic compounds and the like.
  • Polyalkylene oxides are polyalkylene oxides and derivatives thereof, and are, for example, Japanese Patent Application Laid-Open No. 60-37836, Japanese Patent Application Laid-Open No. 1-437790, Japanese Patent Application Laid-Open No. 63-128088, Japanese Patent Application Laid-Open No. 3-167279. Examples thereof are those disclosed in Japanese Patent Publication No. 4386193, US Pat. No. 4,424,327, and the like.
  • polyalkylene oxides such as diethylene glycol, triethylene glycol, polyethylene glycol, and polypropylene glycol
  • polyethylene glycol monoalkyl ester such as diethylene glycol, triethylene glycol, polyethylene glycol, and polypropylene glycol
  • polyethylene glycol dialkyl ester such as diethylene glycol dialkyl ester
  • polypropylene glycol dialkyl ester diethylene glycol monoalkyl ether
  • diethylene glycol examples thereof include derivatives of polyalkylene oxides such as dialkyl ether, dipropylene glycol monoalkyl ether and dipropylene glycol dialkyl ether.
  • crown ethers include those disclosed in Japanese Patent Application Laid-Open No. 55-2236, Japanese Patent Application Laid-Open No. 3-167279, and the like.
  • sila crown ethers examples include those disclosed in Japanese Patent Application Laid-Open No. 60-168775. Specific examples thereof include dimethyl shira-11-crown-4, dimethyl shira-14-crown-5, dimethyl shira-17-crown-6 and the like.
  • calix allenes examples include those disclosed in Japanese Patent Application Laid-Open No. 60-179482, Japanese Patent Application Laid-Open No. 62-235379, and Japanese Patent Application Laid-Open No. 63-88152.
  • cyclodextrins examples include those disclosed in Japanese Patent Publication No. 5-505835. Specific examples thereof include ⁇ -, ⁇ - or ⁇ -cyclodextrin.
  • examples of the pyrogallol-based cyclic compounds include compounds disclosed in JP-A-2000-191600. Specifically, 3,4,5,10,11,12,17,18,19,24,25,26-dodecaethoxycarbomethoxy-C-1, C-8, C-15, C-22- Examples thereof include tetramethyl [14] metacyclophane. Only one kind of these anionic polymerization accelerators may be used, or two or more kinds thereof may be used in combination.
  • the plasticizer can be contained as long as the effect of the present invention is not impaired.
  • this plasticizer include triethyl acetyl citrate, tributyl acetyl citrate, dimethyl adipate, diethyl adipate, dimethyl sebacate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisodecyl phthalate, dihexyl phthalate, and phthalic acid.
  • Examples thereof include ethylhexylcyclohexylcarboxylate, diisobutyl fumarate, diisobutyl maleate, triglyceride caproate, 2-ethylhexyl benzoate, dipropylene glycol dibenzoate and the like.
  • tributyl acetylcitrate, dimethyl adipate, dimethyl phthalate, 2-ethylhexyl benzoate, and dipropylene glycol are excellent in compatibility with 2-cyanoacrylic acid ester and high plasticization efficiency.
  • Dibenzoate is preferred. Only one of these plasticizers may be used, or two or more of these plasticizers may be used in combination.
  • the content of the plasticizer is not particularly limited, but when the total content of the methylene malonate compound and the 2-cyanoacrylate compound is 100 parts by mass, it is preferably 3 parts by mass to 50 parts by mass, more preferably. It is 10 parts by mass to 45 parts by mass, more preferably 20 parts by mass to 40 parts by mass. When the content of the plasticizer is 3 parts by mass to 50 parts by mass, the retention rate of the adhesive strength after the cold heat resistance cycle test can be improved.
  • thickener polymethyl methacrylate, a polymer of methyl methacrylate and an acrylic acid ester, a polymer of methyl methacrylate and another methacrylic acid ester, acrylic rubber, polyvinyl chloride, polystyrene, etc.
  • acrylic rubber polyvinyl chloride, polystyrene, etc.
  • examples thereof include cellulose ester, polyalkyl-2-cyanoacrylic acid ester and ethylene-vinyl acetate copolymer. Only one of these thickeners may be used, or two or more of these thickeners may be used in combination.
  • the curable composition of the present invention may also contain fumed silica as a filler or the like.
  • This fumed silica is an anhydrous silica of ultrafine powder (preferably having a primary particle diameter of 500 nm or less, particularly preferably 1 nm to 200 nm), and this anhydrous silica is, for example, made of silicon tetrachloride as a raw material and in a high temperature flame.
  • Ultrafine powder (preferably with a primary particle size of 500 nm or less, particularly preferably 1 nm to 200 nm) produced due to oxidation in the vapor phase state, which is highly hydrophilic hydrophilic silica and hydrophobic.
  • There is highly hydrophobic silica. Any of these fumed silica can be used, but hydrophobic silica is preferable from the viewpoint of good dispersibility in the methylene malonate compound.
  • hydrophilic silica various commercially available products can be used, and examples thereof include Aerosil 50, 130, 200, 300 and 380 (these are trade names and are manufactured by Nippon Aerosil Co., Ltd.).
  • the specific surface areas of these hydrophilic silicas are 50 ⁇ 15 m 2 / g, 130 ⁇ 25 m 2 / g, 200 ⁇ 25 m 2 / g, 300 ⁇ 30 m 2 / g, and 380 ⁇ 30 m 2 / g, respectively.
  • As commercially available hydrophilic silica Leoloseal QS-10, QS-20, QS-30, QS-40 (these are trade names and manufactured by Tokuyama Corporation) and the like can be used.
  • hydrophilic silicas are 140 ⁇ 20 m 2 / g, 220 ⁇ 20 m 2 / g, 300 ⁇ 30 m 2 / g, and 380 ⁇ 30 m 2 / g, respectively.
  • commercially available hydrophilic silica manufactured by CABOT or the like can also be used.
  • hydrophobic silica a compound capable of reacting with a hydroxy group existing on the surface of the hydrophilic silica to form a hydrophobic group, or being adsorbed on the surface of the hydrophilic silica can form a hydrophobic layer on the surface.
  • Products produced by contacting the compound with hydrophilic silica in the presence or absence of a solvent, preferably heating and treating the surface of the hydrophilic silica can be used.
  • Compounds used to surface-treat hydrophilic silica to make it hydrophobic include various alkyl, aryl, and aralkyl silane coupling agents having a hydrophobic group such as n-octyllialkoxysilane, methyltrichlorosilane, and dimethyldi. Examples thereof include silylating agents such as chlorosilane and hexamethyldisilazane, silicone oils such as polydimethylsiloxane, higher alcohols such as stearyl alcohol, and higher fatty acids such as stearic acid.
  • a product hydrophobized with any compound may be used.
  • hydrophobic silica includes, for example, Aerosil RY200, R202, which has been surface-treated with silicone oil and hydrophobized, and Aerosil R974, R972, R976, n-octyltri, which has been surface-treated with a dimethylsilylating agent.
  • Examples thereof include Leolosil MT-10 (trade name, Tokuyama Co., Ltd.) which has been surface-treated with chlorosilane and hydrophobized.
  • hydrophobic silicas are 100 ⁇ 20 m 2 / g, 100 ⁇ 20 m 2 / g, 170 ⁇ 20 m 2 / g, 110 ⁇ 20 m 2 / g, 250 ⁇ 25 m 2 / g, 150 ⁇ 20 m 2, respectively.
  • / G 150 ⁇ 20m 2 / g, 260 ⁇ 20m 2 / g, 120 ⁇ 10m 2 / g.
  • the preferable content of fumed silica in the curable composition of the present invention is 1 part by mass to 30 parts by mass when the total content of the methylene malonate compound and the 2-cyanoacrylate compound is 100 parts by mass. ..
  • the preferable content of this fumed silica depends on the type of methylene malonate compound, the type of fumed silica, etc., but is 1 part by mass to 25 parts by mass, and a particularly preferable content is 2 parts by mass to 20 parts by mass. It is a mass part. Within the above range, an adhesive composition having good workability can be obtained.
  • the method for producing the curable composition of the present invention is not particularly limited and may be produced by mixing the above-mentioned components, but the mixture is mixed in an atmosphere free of or little moisture and oxygen (for example, 0.01% by volume or less). It is preferable to mix them in an inert gas atmosphere. Examples of the inert gas include nitrogen and argon. Further, the method for producing a curable composition of the present invention is preferably carried out under light shielding.
  • the mixing method is not particularly limited, and a known mixing method can be used.
  • the curable composition of the present invention may be stored by a known storage method, and may be stored in an atmosphere free or low in humidity and oxygen (for example, 0.01% by volume or less). Alternatively, it is preferably stored in a closed container, and more preferably stored in an inert gas atmosphere or stored in a closed container. Examples of the inert gas include nitrogen and argon. Further, the curable composition of the present invention is preferably stored under light shielding.
  • the curing method of the curable composition of the present invention is not particularly limited as long as it can be polymerized and cured by a methylene malonate compound, and may be cured by moisture such as humidity or by light. It is preferable to cure with moisture such as.
  • the curable composition of the present invention is cured by light, it is cured by irradiating ultraviolet rays or visible light using a high-pressure mercury lamp, a halogen lamp, a xenon lamp, an LED (light emitting diode) lamp, sunlight or the like. be able to.
  • the curable composition of the present invention can be used for known curable compositions.
  • it can be suitably used as a so-called instant adhesive.
  • the curable composition of the present invention has moisture curability and excellent storage stability, it can be used in a wide range of fields such as general use, industrial use and medical use. Examples thereof include, but are not limited to, adhesives, coating agents (protective coating agents, etc.), printing inks (inkjet ink, etc.), photoresists, sealing agents, and the like.
  • sealing of electronic parts attachment of reel sheets and threading guides on fishing rods, fixing of wire rods such as coils, fixing of magnetic heads to pedestals, filling used for tooth treatment.
  • It can be suitably used for adhesion, fixing, or coating between the same or different kinds of articles such as agents, adhesion and decoration of artificial nails, and the like.
  • the curable composition of the present invention can be preferably used in the first embodiment of the method for producing an adhesive of the present invention shown below.
  • the first embodiment of the method for producing an adhesive of the present invention is also referred to as a step of applying the curable composition of the present invention to the surface of the first adhesive to be adhered (hereinafter, also referred to as a "curable composition applying step”. ), A step of adhering the surface of the first adherend to which the curable composition is applied and the surface of the second adherend to obtain an adhesive (hereinafter, also referred to as "first adhesion step"). ) Is included.
  • the curing type composition of the present invention may be applied only to the surface of one adherend (the surface of the first adherend), or one side.
  • the curable composition of the present invention is applied to both the surface of the object to be adhered (the surface of the first object to be adhered) and the surface of the other object to be adhered (the surface of the second object to be adhered). May be good. Further, even if the surface of the first object to be adhered and the surface of the second object to be adhered are partially different surfaces of the object to be adhered, two places that can be adhered to each other in one object to be adhered. It may be the face of.
  • the shape of the surface of the first adherend and the surface of the second adhered is not particularly limited and may be any shape such as a flat surface, an uneven surface, and an irregularly shaped surface.
  • Examples of the material of the adherend include plastic, rubber, wood, metal, inorganic material, paper and the like.
  • plastics include cyclic polyolefins having cyclic olefins such as polyvinyl alcohol, triacetyl cellulose, diacetyl cellulose and other cellulose acetate resins, acrylic resins, polyethylene terephthalates, polycarbonates, polyarylates, polyether sulfone and norbornene as monomers. Examples thereof include resins, polyvinyl chlorides, epoxy resins, and polyurethane resins.
  • Specific examples of rubber include natural rubber, styrene-butadiene rubber (SBR), and the like.
  • SBR styrene-butadiene rubber
  • wood include natural wood and synthetic wood.
  • the metal include steel plates, metals such as aluminum and chromium, and metal oxides such as zinc oxide (ZnO) and indium tin oxide (ITO).
  • the inorganic material include glass, mortar, concrete, stone and the like.
  • Specific examples of paper include high-quality paper, coated paper, art paper, imitation paper, thin paper, thick paper and other papers, and various synthetic papers.
  • the method of applying the cured type composition to the surface of the adherend is not particularly limited.
  • the applying method include a method using an applying tool such as a brush, a spatula, a cotton swab, a roller, and a spray, and a bar coater, an applicator, a doctor blade, a dip coater, a roll coater, a spin coater, a flow coater, and a knife.
  • Examples thereof include a method of coating with a coating machine such as a coater, a comma coater, a reverse roll coater, a die coater, a lip coater, a spray coater, a gravure coater, a micro gravure coater and a dispenser.
  • a coating machine such as a coater, a comma coater, a reverse roll coater, a die coater, a lip coater, a spray coater, a gravure coater, a micro gravure coater and a dispenser.
  • the surface of the first adherend and the surface of the second adherend are bonded together, and the curable composition of the present invention is cured to obtain an adhesive. ..
  • the first bonding step it is possible to cure even at room temperature (for example, 10 ° C. to 35 ° C.), but in order to accelerate the curing, the surface of the first adherend, the second The surface of the adherend and / or the adherend may be heated.
  • the heating temperature may be a range that does not affect the adherend, for example, heating to about 35 ° C. to 100 ° C. for curing.
  • pressure is applied in the direction in which the surface of the first object to be adhered and the surface of the second object to be adhered overlap each other until the bonding is completed. You may call it.
  • the two-component curable composition set of the present invention contains a composition A containing a 2-cyanoacrylate compound and a composition B containing a Lewis acidic compound, and is at least one of the composition A and the composition B. However, it further contains a methylene malonate compound.
  • the composition A and the composition B are applied to the surface of the object to be adhered, and preferably the composition A and the composition B are applied or adhered to the surface of one of the objects to be adhered.
  • the composition A is applied to the surface of one object to be adhered
  • the composition B is applied to the surface of the other object to be adhered
  • the solvent is removed as necessary, and the surfaces of the two objects to be adhered are removed. Can be overlapped and cured and adhered.
  • a preferred embodiment of the methylene malonate compound of the composition A and a preferred embodiment of the Lewis acidic compound of the composition B in the two-component curable composition set of the present invention are described above, except as described later. It is the same as the preferred embodiment of the methylene malonate compound and the preferred embodiment of the Lewis acidic compound in the curable composition of the present invention.
  • the methylene malonate compound may be contained in either one of the composition A or the composition B, or may be contained in both.
  • the composition A and the composition B in the two-component curable composition set of the present invention may independently contain the polymerization inhibitor and / or the other components.
  • a preferred embodiment of the polymerization inhibitor and the other component in the two-component curable composition set of the present invention is the polymerization inhibitor and the other component in the above-mentioned curable composition of the present invention. Similar to the preferred embodiment.
  • the content of the 2-cyanoacrylate compound in the composition A is determined from the viewpoint of heat resistance of the obtained cured product and curing uniformity. It is preferably 1% by mass to 99% by mass, more preferably 5% by mass to 95% by mass, further preferably 10% by mass to 90% by mass, and 20% by mass with respect to the total solid content of the above. It is particularly preferably% to 80% by mass, and most preferably 30% by mass to 70% by mass.
  • the content of the methylene malonate compound in the composition A is the same as that of the composition A from the viewpoint of heat resistance of the obtained cured product and curing uniformity.
  • It is preferably 1% by mass to 99% by mass, more preferably 5% by mass to 95% by mass, still more preferably 10% by mass to 90% by mass, and 20% by mass with respect to the total solid content. It is particularly preferably about 80% by mass, and most preferably 30% by mass to 70% by mass.
  • the content of the 2-cyanoacrylate compound in the composition A may be 50% by mass to 100% by mass with respect to the total solid content of the composition A. It is preferably 80% by mass to 100% by mass, more preferably 90% by mass to 100% by mass, and particularly preferably 95% by mass to 100% by mass.
  • the content of the Lewis acidic compound in the composition B is determined from the viewpoint of heat resistance, curing uniformity, and curing rate of the obtained cured product.
  • the total content of the methylene malonate compound in A and the composition B is preferably 0.001 part by mass to 1.0 part by mass, preferably 0.001 part by mass to 0.5 part by mass, based on 100 parts by mass. It is more preferably 0.001 part by mass to 0.1 part by mass.
  • the content of the methylene malonate compound in the composition B is the same as that of the composition A from the viewpoint of heat resistance of the obtained cured product and curing uniformity. It is preferably 1% by mass to 99% by mass, more preferably 5% by mass to 95% by mass, and particularly preferably 10% by mass to 90% by mass with respect to the total solid content.
  • the content of the Lewis acidic compound in the composition B is preferably 1% by mass to 100% by mass with respect to the total solid content of the composition B. It is more preferably 10% by mass to 100% by mass, and particularly preferably 50% by mass to 100% by mass.
  • the composition B preferably contains a solvent.
  • the solvent those mentioned above in the curable composition of the present invention are preferably mentioned.
  • the content of the solvent in the composition B is preferably 10% by mass to 99.99% by mass, preferably 50% by mass, based on the total mass of the composition B. It is more preferably from mass% to 99.9% by mass, and particularly preferably from 80% by mass to 99% by mass.
  • the value of the mass ratio (Mc / Mm) of the total content Mc of the 2-cyanoacrylate compound in the composition A and the total content Mm of the methylene malonate compound in the composition A and the composition B is From the viewpoint of heat resistance of the obtained cured product and curing uniformity, it is preferably 0.05 to 20, more preferably 0.1 to 10, and 0.2 to 5. It is more preferably 0.5 to 2, and particularly preferably 0.5 to 2.
  • the two-component curable composition set of the present invention may contain a composition or an article other than the composition A and the composition B.
  • the composition other than the composition A and the composition B is not particularly limited, but for example, a cleaning liquid on the surface of the adherend to which the composition A and / or the composition B is applied, the composition A. And a liquid for removing the cured product of the composition B and the like.
  • the article is not particularly limited, but for example, a brush, a spatula, a cotton swab, a roller, a spray or the like to which the composition A or the composition B is applied, an extra composition A and the above. Examples thereof include a removing tool such as paper and cloth for removing the composition B.
  • the composition B containing a Lewis acidic compound is first adhered to the composition B.
  • the surface of the first adherend and the surface of the second adherend to which the composition A is applied are adhered to each other, or the first surface to which the composition A and the composition B are applied.
  • a step of adhering the surface of the object to be adhered and the surface of the second object to be adhered to obtain an adhesive, and at least one of the composition A and the composition B further contains a methylene malonate compound. ..
  • composition A and the composition B in the method for producing an adhesive of the present invention are the preferred embodiments of the composition A and the composition B in the above-mentioned two-component curable composition set of the present invention. The same is true.
  • composition B imparting step and composition A imparting step The method for producing an adhesive of the present invention includes a step of applying a composition B containing a Lewis acidic compound to the surface of a first adherend (also referred to as a “composition B application step”), and a methylene malonate compound.
  • composition B application step also referred to as a “composition B application step”
  • composition A application step also referred to as “composition A application step”.
  • the composition B application step and the composition A application step may be performed first or at the same time.
  • both the composition A and the composition B are applied to the surface of one object to be adhered (the surface of the first object to be adhered), and the other is coated.
  • the composition A and / or the composition B may be applied to the surface of the adhesive (the surface of the second adherend), or the surface of one adherend (the first surface of the adherend).
  • the composition A may be applied to the surface of the object to be adhered), and the composition B may be applied to the surface of the other object to be adhered (the surface of the second object to be adhered).
  • the surface of the first object to be adhered and the surface of the second object to be adhered are partially different surfaces of the object to be adhered, two places that can be adhered to each other in one object to be adhered. It may be the face of.
  • the shape of the surface of the first adherend and the surface of the second adhered is not particularly limited and may be any shape such as a flat surface, an uneven surface, and an irregularly shaped surface.
  • the amount of the composition A to be applied in the step of applying the composition A is not particularly limited and may be any amount as long as it can be adhered, and can be appropriately selected as desired. Further, after the composition A is applied, the solvent may be removed by air drying, heat drying or the like, if necessary.
  • the amount of the composition B applied in the step of applying the composition B is not particularly limited as long as it can be adhered, but the amount of the Lewis acidic compound contained in the composition B is not particularly limited. It is preferably 0.001 part by mass to 1.0 part by mass, preferably 0.001 part by mass to 1.0 part by mass, based on 100 parts by mass of the total amount of the methylene malonate compound added by the composition A and the composition B in the application step. It is more preferably 0.5 parts by mass, and particularly preferably 0.001 parts by mass to 0.1 parts by mass. Further, after the composition B is applied, the solvent may be removed by air drying, heat drying or the like, if necessary.
  • the application method used in the composition B application step and the composition A application step is not particularly limited, and the composition B or the composition A is subjected to the same method as the curable composition application step. It can be applied to the surface of the first adherend or the surface of the second adherend.
  • the surface of the first adherend to which the composition B is applied is bonded to the surface of the second adherend to which the composition A is applied.
  • a step of adhering the surface of the first adherend to which the composition A and the composition B are applied and the surface of the second adherend to obtain an adhesive also referred to as "second adhesion step").
  • the surface of the first object to be bonded and the surface of the second object to be bonded may be overlapped and bonded.
  • the Lewis acidic compound contained in the composition B acts on the methylene malonate compound contained in the composition A and / or the composition B, and the 2-cyanoacrylate compound and the above are affected by moisture in the air or the like.
  • the methylene malonate compound is copolymerized and cured to bond the surface of the first adherend to the surface of the second adherend.
  • the surface of the first adherend and the surface of the second adhered are overlapped, the surface of the first adhered and / or the surface of the second adhered is, if necessary.
  • the surface may be moved to promote mixing of the composition A and the composition B. Further, in the second bonding step, it is possible to cure even at room temperature (for example, 10 ° C.
  • the surface of the first adherend, the second The surface of the adherend and / or the adherend may be heated.
  • the heating temperature may be a range that does not affect the adherend, for example, heating to about 35 ° C. to 100 ° C. for curing.
  • pressure is applied in the direction in which the surface of the first object to be adhered and the surface of the second object to be adhered overlap each other until the bonding is completed. You may call it.
  • the curable composition of the present invention, the two-component curable composition set of the present invention, or the adherend to be adhered by the method for producing an adhesive of the present invention is not particularly limited and may be an inorganic compound. , It may be an organic compound, an inorganic-organic composite, the same material, or a different material. Further, the curable composition of the present invention, the two-component curable composition set of the present invention, or the method for producing an adhesive of the present invention can adhere a solid form of any shape. Examples of the adherend include the same materials as described above.
  • Diethyl methylene malonate (hereinafter, also referred to as “DEMM”) produced according to the following literature was used. Purity: 99% by mass or more (from 1 1 H-NMR). Journal of the Japanese Society of Chemistry, 1972, No. Pages 3, 596-598
  • composition A1 Ethyl 2-cyanoacrylate and diethyl methylenemalonate were mixed at a mass ratio of 5: 5 to prepare composition A1.
  • composition A2 Ethyl 2-cyanoacrylate and diethyl methylenemalonate were mixed at a mass ratio of 9: 1 to prepare composition A2.
  • composition A3 Ethyl 2-cyanoacrylate and diethyl methylenemalonate were mixed at a mass ratio of 1: 9 to prepare composition A3.
  • composition A4 Ethyl 2-cyanoacrylate and di-t-butyl methylenemalonate were mixed at a mass ratio of 5: 5 to prepare composition A3.
  • composition B1 As a Lewis acidic compound, zinc (II) trifluoromethanesulfonate was added to acetone so as to have a concentration of 0.15 mmol / L and completely dissolved to prepare a composition B1.
  • composition B2 As a Lewis acidic compound, ytterbium (III) trifluoromethanesulfonate was added to acetone so as to have a concentration of 0.15 mmol / L and completely dissolved to prepare each composition B2.
  • composition B3 As a Lewis acidic compound, zinc (II) acetylacetonate was added to acetone so as to have a concentration of 0.15 mmol / L and completely dissolved to prepare a composition B3.
  • composition B4 As a Lewis acidic compound, iron (II) trifluoromethanesulfonate was added to acetone so as to have a concentration of 0.15 mmol / L and completely dissolved to prepare a composition B2.
  • Example 1 200 ⁇ L of composition A1 and 20 ⁇ L of composition B1 were mixed to obtain a mixture (curable composition).
  • the liquid stability of the obtained mixture was good without thickening for more than 1 hour after mixing at room temperature (25 ° C.).
  • TG / DTA ⁇ Thermogravimetric / differential thermal (TG / DTA) measurement> To the obtained mixture was added 1 ⁇ L of a 25 mass% ethanol solution of dimethyl-p-toluidine and cured. The obtained cured product was subjected to TG / DTA measurement at a temperature rise of 20 ° C./min under a nitrogen atmosphere using a TG / DTA measuring device (STA 2500 manufactured by Netch Co., Ltd.). The measurement results are shown in Table 1 and FIG.
  • Example 2 A curable composition of Example 2 was prepared in the same manner as in Example 1 except that the composition B2 was used instead of the composition B1.
  • the liquid stability of the obtained mixture was good without thickening for more than 1 hour after mixing at room temperature (25 ° C.).
  • monomer reaction rate measurement, TG / DTA measurement, and set time measurement were performed, respectively.
  • the evaluation results are summarized in Table 1 and FIG.
  • Example 3 A curable composition of Example 3 was prepared in the same manner as in Example 1 except that the composition A2 was used instead of the composition A1. The liquid stability of the obtained mixture was good without thickening for more than 1 hour after mixing at room temperature (25 ° C.). Using the obtained cured composition, monomer reaction rate measurement and TG / DTA measurement were performed. The evaluation results are shown in Table 1 and FIG.
  • Example 4 A curable composition of Example 4 was prepared in the same manner as in Example 3 except that the composition B2 was used instead of the composition B1. The liquid stability of the obtained mixture was good without thickening for more than 1 hour after mixing at room temperature (25 ° C.). Using the obtained cured composition, monomer reaction rate measurement and TG / DTA measurement were performed. The evaluation results are shown in Table 1 and FIG.
  • Example 5 A curable composition of Example 5 was prepared in the same manner as in Example 1 except that the composition A3 was used instead of the composition A1. The liquid stability of the obtained mixture was good without thickening for more than 1 hour after mixing at room temperature (25 ° C.). Using the obtained cured composition, monomer reaction rate measurement and TG / DTA measurement were performed. The evaluation results are shown in Table 1 and FIG.
  • Example 6 A curable composition of Example 6 was prepared in the same manner as in Example 5 except that the composition B2 was used instead of the composition B1. The liquid stability of the obtained mixture was good without thickening for more than 1 hour after mixing at room temperature (25 ° C.). Using the obtained cured composition, monomer reaction rate measurement and TG / DTA measurement were performed. The evaluation results are shown in Table 1 and FIG.
  • Example 7 A curable composition of Example 7 was prepared in the same manner as in Example 1 except that the amount of the composition B1 used was changed so that the amount of the Lewis acidic compound shown in Table 1 was added. The liquid stability of the obtained mixture was good without thickening for more than 1 hour after mixing at room temperature (25 ° C.). Using the obtained cured composition, the monomer reaction rate and the set time were measured, respectively. The evaluation results are summarized in Table 1.
  • Example 8 A curable composition of Example 8 was prepared in the same manner as in Example 1 except that the composition B3 was used instead of the composition B1. The liquid stability of the obtained mixture was good without thickening for more than 1 hour after mixing at room temperature (25 ° C.). Using the obtained cured composition, the monomer reaction rate and the set time were measured. The evaluation results are shown in Table 1.
  • Example 9 A curable composition of Example 9 was prepared in the same manner as in Example 1 except that the composition B4 was used instead of the composition B1. The liquid stability of the obtained mixture was good without thickening for more than 1 hour after mixing at room temperature (25 ° C.). Using the obtained cured composition, the monomer reaction rate and the set time were measured. The evaluation results are shown in Table 1.
  • Example 10 A curable composition of Example 10 was prepared in the same manner as in Example 1 except that the composition A4 was used instead of the composition A1. The liquid stability of the obtained mixture was good without thickening for more than 1 hour after mixing at room temperature (25 ° C.). Using the obtained cured composition, the monomer reaction rate and the set time were measured. The evaluation results are shown in Table 1.
  • Example 11 A curable composition of Example 11 was prepared in the same manner as in Example 1 except that the amount of the composition B1 used was changed so that the amount of the Lewis acidic compound shown in Table 1 was added. The liquid stability of the obtained mixture was good without thickening for more than 1 hour after mixing at room temperature (25 ° C.). Using the obtained cured composition, the monomer reaction rate and the set time were measured. The evaluation results are shown in Table 1.
  • Comparative Example 1 A curable composition of Comparative Example 1 was prepared in the same manner as in Example 1 except that only ethyl 2-cyanoacrylate was used instead of the composition A1 and the composition B1 was not used. The liquid stability of the obtained mixture was good without thickening for more than 1 hour after mixing at room temperature (25 ° C.). Using the obtained cured composition, monomer reaction rate measurement, TG / DTA measurement, and set time measurement were performed, respectively. The evaluation results are shown in Table 1, FIG. 1 and FIG.
  • Comparative Example 2 A curable composition of Comparative Example 2 was prepared in the same manner as in Example 1 except that the composition A2 was used instead of the composition A1 and the composition B1 was not used. The liquid stability of the obtained mixture was good without thickening for more than 1 hour after mixing at room temperature (25 ° C.). Using the obtained cured composition, monomer reaction rate measurement, TG / DTA measurement, and set time measurement were performed, respectively. The evaluation results are shown in Table 1, FIG. 1 and FIG.
  • CA ethyl 2-cyanoacrylate
  • DEMM diethyl methylenemalonate
  • DtBMM di-t-butyl methylenemalonate
  • ABS acrylonitrile-butadiene-styrene copolymer. Represents.
  • the curable compositions of Examples 1 to 6 are superior in heat resistance of the obtained cured product as compared with the curable compositions of Comparative Examples 1 and 2. Further, the cured compositions of Examples 7 to 11 have higher heat resistance of the obtained cured product than the cured compositions of Comparative Example 1 or 2 although the measurement data of the above TG / DTA measurement is not specified. Excellent.

Abstract

L'invention concerne une composition durcissable comprenant un composé malonate de méthylène, un composé 2-cyanoacrylate et un composé acide de Lewis. Le composé de malonate de méthylène est de préférence un composé représenté par la formule (1) ou la formule (2). Dans la formule (1) et la formule (2), chacun de X1 à X4 représente indépendamment O, NR ou C(R)2, chaque R représente indépendamment un atome d'hydrogène, un groupe alkyle ou un groupe aryle, R1 et R2 représentent chacun indépendamment un groupe alkyle ou un groupe aryle et R3 représente un groupe alkylène, un groupe arylène ou un groupe qui est une combinaison d'au moins deux groupes alkylène et groupes arylène.
PCT/JP2020/034364 2019-09-10 2020-09-10 Composition durcissable, ensemble de compositions durcissables à deux liquides et procédé de production d'article lié WO2021049589A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014503474A (ja) * 2010-10-20 2014-02-13 バイオフオーミツクス・インコーポレイテツド エネルギー移動手段の存在下での急速回収を用いたメチレンマロナートの合成
JP2016515153A (ja) * 2013-03-15 2016-05-26 ヘンケル アイピー アンド ホールディング ゲゼルシャフト ミット ベシュレンクテル ハフツング 二成分系シアノアクリレート／カチオン硬化性接着剤システム
WO2018022810A1 (fr) * 2016-07-26 2018-02-01 Ppg Industries Ohio, Inc. Compositions durcissables contenant des composés vinyliques 1,1-di-activés, et revêtements et procédés associés
WO2018212330A1 (fr) * 2017-05-18 2018-11-22 ナミックス株式会社 Composition de résine
US20200190335A1 (en) * 2018-12-17 2020-06-18 Sirrus, Inc. Surface treatment methods for compositions having 1,1-disubstituted alkene compounds

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014503474A (ja) * 2010-10-20 2014-02-13 バイオフオーミツクス・インコーポレイテツド エネルギー移動手段の存在下での急速回収を用いたメチレンマロナートの合成
JP2016515153A (ja) * 2013-03-15 2016-05-26 ヘンケル アイピー アンド ホールディング ゲゼルシャフト ミット ベシュレンクテル ハフツング 二成分系シアノアクリレート／カチオン硬化性接着剤システム
WO2018022810A1 (fr) * 2016-07-26 2018-02-01 Ppg Industries Ohio, Inc. Compositions durcissables contenant des composés vinyliques 1,1-di-activés, et revêtements et procédés associés
WO2018212330A1 (fr) * 2017-05-18 2018-11-22 ナミックス株式会社 Composition de résine
US20200190335A1 (en) * 2018-12-17 2020-06-18 Sirrus, Inc. Surface treatment methods for compositions having 1,1-disubstituted alkene compounds

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